Polyhalomethane-unsaturated acid reaction products



Patented Sept. 14, 1954 POIIYHALOMETH-ANE-UNSATURATED ACID REAGTIGNPRODUCTS Lyle A. Hamilton, Pitman, and Charles F. Feasley,

Wocdbury, N. 1., assignors to Socony-Vacuum Oil Company, Incorporated, acorporation of? New York No Drawing.

Original application June-23; 1948;

Serial No. 34,827. Divided and this application; December 23, 1949,Serial No'. 134,842

6- Claims. 1

This invention relates to new chemical com positions or reaction.products and is more particularly related to a novel group or class ofreaction products which are especially valuable as extreme pressureaddition agents in lubricating compositions. The new products are alsouseful chemical intermediates from which other extreme pressurelubricant assistants can be prepared.

It is well known to those familiar with the art that a lubricating oil"such as a mere refined petroleum oil fraction is incapable ofmaintaining a lubricating filmbetween engaged metallic surfaces wheretheunit load at the engaged surfaces exceeds a pressure of say 3000-4000pounds per square inch. In various types of modern machinery, such asthe hypoid gears used in motor vehicles, the engaging pressures betweenthe gear teeth are sohigh that ordinary lubricating oilsalone'a'reincapable of properly lubri eating them, the abnormally high pressuresgenerally causing seriousrupture of the oil film. To overcome thisproblem, special extreme pressure type lubricants have been developed.These lubricants are prepared by incorporating into a petroleumlubricating oil, or other suitable carrying-agent, an additiveingredient which willform a lubricant film capable of withstanding theseabnormally highpressures.

dients or extreme pressure (E. P.) lubricant base'sand the lubricantcompositions compounded with minor proportions of: such ingredients areknown as E. P. lubricants. have been proposed for use as E. P. bases.Among. such materials are various types of halogen-containing compounds.The present inven tion is concerned. with E. P. bases of this type.

It is an" object. of this invention to provide a novel class ofcompounds which are valuable base ingredients for extreme pressurelubricants. A further object is the provision of extremepressurelubricants characterized. by the presence therein of these.ingredientaeither alone or in combination with other ingredients. Astill furtherobject is; the provision of a methodior preparing theselubricants. Other objects and advantages will appear hereinafter;

This invention is based upon the discovery that novel lubricants, havingexceptional ability to Ingredients of this character are known asextreme pressure ingre- I Numerous materials lubricate effectively underconditions of extreme pressure loading may be produced by incorporatingwith a hydrocarbon. lubricant oil a, small proportion of. a compound of.the general formula where R is selected from the=groupconsisting ofhydrogen, alkyl and alkenyl radicals, R. isselected from the groupconsisting of hydrogen, hydrocarbon, metal and basioion, m is an integerfrom 4- to 1-3, n is an integer from 1 to 3, and.

where A and B together make up a polyhalomethane.

The polyhalogenated" acids and esters contem plated by the inventionare: prepared. by reaction of a polyhalomethane, such as. carbon tetra--chloride, chloroform orbromotrichloromethane, with an unsaturatedorganic. acid or ester of: the general'formula R--CI-IL=CH'-(CH2.)mCOOR'wherein R is selected; from the group consisting of hydrogen, alkyl andalkenyl; R is selected from the group. consisting. of, hydrogen andhydrocarbon radicals, and m is a whole number from 4 to 13. When Bishydrogen, A inthe preceding general formula. would be thecarbon-containing. fragment ofl the. polyhalomethane (directiveaddition) and" a single product would be formed. However, when R isalkyLthe carboncontaining. fragment of the polyhalomethane would bepartially A and partially 3' (random addition) and" two isomericproducts would be formed. If an ester is desired as the final prodnot,an unsaturated ester may be used as the starting reactant in place ofthe acid, or the acid may be used and" the product esterified.

Among the unsaturated acids which may be reacted with the.polyhalomethanes to produce the new products of" the invention thefollowing may be mentioned as non-limiting examples: 6,7-heptenoic acid,9,10-dec'enoic (caproleic) acid, 9',10-undecylenic acid,10,1l-undecy1enic acid, 9,10-dodeoenoic (lauroleic) acid, 9,l0-tetra--decenoic (myristol'eicl' acid, 9,10-hexadecenoic (palmitoleic) acid,6,7-octadec'enoic (petroselinicy acid, 9,10-octadecenoic (oleic): acid,ll,l2-octa. decenoic (vaccenic)= acid, 13,14. docosenoic (erucic) acid,15,16-tetracosenoic (selacholeic) acid, 9,10,12,13-octadecenoic(linoleic) acid, and

3 9,10,11,l2,13,14-octadecatrienoic acid.

Where it is desired to produce a polyhalogenated ester, the esters ofany of the foregoing acids may be utilized in the reaction with thepolyhalomethane compound. Specific examples of suitable esters are:octadecyl ester of 6,7-heptenoic acid, methyl ester of 9,10-decenoicacid, butyl ester of 9,10-dodecenoic acid, hexadecyl ester of9,10-undecylenic acid, amyl ester of 10,1l-undecylenic acid, octadecylester of 10,11- undecylenic acid, tetradecyl ester of 9,10-tetradecenoicacid, hexyl ester of 6,7 -octadecenoic acid, methyl ester of6,7-octadecenoic acid, amyl ester of 9,10-octadecenoic acid, methylester of 11,12-octadecenoic acid, dodecyl ester of 13.14- docosenoicacid, methyl ester of 15,16-tetracosenoic acid, amyl ester of9,10,12,13-octadecenoic acid and undecyl ester of 9,10,11,l2,13,14-octadecatrienoic acid.

The reaction between the polyhalomethane and the unsaturated acid orester is effected in the presence of a free radical-forming compound asa catalyst. For this purpose benzoyl peroxide, diacetyl peroxide, alkylacyl peroxides, hydroperoxides and ditertiary butyl peroxides may bementioned as specific examples. Of these, benzoyl peroxide isparticularly preferred.

The reaction conditions required for the preparation of our novelcompounds are essentially those described in the article by M. S.Kharasch et al. (Science, vol. 102 (1945), p. 128) relating to theaddition of carbon tetrachloride and chloroform to olefins. Thus, thereaction is readily effected by adding to the unsaturated acid, orester, an excess of the polyhalomethane and a small amount, about0.02inol of the peroxide catalyst, and heating the reaction mixture.Preferred reaction temperatures are those obtained by heating at thereflux temperatures of the reaction mixtures, although broadly,temperatures falling within the range varying between about 30 C. andabout 100 C. are entirely satisfactory.

We have found that the reaction conditions vary somewhat depending onthe particular polyhalomethane reactant employed, since these compoundsvary noticeably in reactivity. Thus, we have found thatbromotrichloromethane reacts most readily. Accordingly, with thiscompound as the polyhalomethane, the reaction times are relativelyshort, i. e. from about 5-10 minutes to about one hour. Also, althoughordinarily the amount of peroxide catalyst used may vary from about0.001 mol to about 0.5 mol per mol of unsaturated acid or ester withbromotrichloromethane the amount required is in the lower end of thisrange. In fact, we have found that bromotrichloromethane will reactwithout a peroxide catalyst under the influence of ultraviolet light.

On the other hand, with carbon tetrachloride, and particularly withchloroform, the required reaction times are greatly increased, rangingbroadly from several hours to upwards of 100 hours. Also, the amount oforganic peroxide catalyst required is in the higher end of the aforesaidrange, i. e. from about 0.01 mol to about 0.5 mol per mol of acid, orester, reactant.

The proportions of reactants employed in preparing the reaction productsof the invention may be varied considerably. However, it is preferableto employ an excess of the polyhalomethane reactant. We have found thatthe use of at least about 4 mols of polyhalomethane to 1 mol of theunsaturated acid in the reaction is particularly advantageous, sincewhen this ratio of reactants (elaeostearic) is used, polymerization ofthe acid reactant is largely minimized with a corresponding increase inthe yield of the monomeric adduct, the general formula of which is givenhereinabove. Even when this ratio of reactants is employed, however, thereaction products obtained usually contain minor amounts of relativelyhigh molecular weight compounds formed either by polymerization of theacid reactant, or by interaction of the organic peroxide with one orboth of the reactant materials. This is indicated by the fact thatproduct yields greater than that accounted for by the chlorine contentof the products are obtained where the polyhalomethane reactant ischloroform and particularly where the relatively larger amounts of theorganic peroxides within the above ranges, are used. However, thereaction products may be readily separated by fractionation, such as bymeans of a molecular still, if the pure materials are desired. In anycase, the reaction products are comprised predominantly of thepolyhalogenated acids or esters and are effective extreme pressureingredients. Accordingly, when the products are to be utilized for thispurpose no purification treatment is necessary.

As indicated by the generic formula given hereinbefore, salts of theaforesaid polyhalogenated acids are also contemplated in the invention.These salts may be prepared by reaction of the acid with a metal oxide,or hydroxide, or with a non-metallic base, such as ammonium hydroxide,or by metathesis with a suitable metal salt, such as a chloride,acetate, nitrate, etc. Metal salts can also be prepared by reactin thesodium salt 01' the acid with an alcohol solution of a salt of thedesired metal. Among the metals contemplated for this purpose are:copper, aluminum, magnesium, calcium strontium,barium, zinc, cadmium,tin, lead, vanadium, chromium, manganese, iron, cobalt and nickel. Ofthese metals zinc, tin and lead are particularly preferred.

Further details as to the procedures which may be utilized insynthesizing the compounds contemplated herein may be obtained from thefollowing illustrative examples describing the preparation of typicalreaction products:

EXAMPLE I Undecylenic acid-43014 product I Found Theory For CHI-11901400OH Percent Chlorine35.7 Negtrglization Number-- Percent Chlorine-42Neutr alization Number-165. 5

EXANIPLE II Preparation of the lead salt of the carbon tetrachlorideundecylenic acid product One hundred and thirty-five grams of theundecylenic acid -CC14 product previously described were mixed with 76grams of Pb (CH3COO) 2.3H2O

enemas-1i Heat: was applied with. stirring until the teme. perature:reached 1 40?- C. Then the condenser was: set downward for distillationand: the acetic acid: and, water distilled out in a stream of nitrogen.The reaction product was flushed clear of: waterand: acetic acid:byblowingwithnitrogenfor onehour; One hundred and sixty-seven grams ofadark orange, very viscous liquid wereobtained; The theoretical yield is176 grams. The product analyzed 24.3% lead and 24 .09% chlorine.Theoretical values for these constitu entsare 24% lead and 32.6%chlorine, respectively. (NorEr-The theoretical values are based on apure undecylenic acid -CC14 product.) However, the undecylenic acidproduct (Example I) was not purified andwas found by actualanalysisto-contain 35.7% chlorine and had an N. N. of 167.8. On the basis ofthis acid, the following comparative values are'given Expected Values(on the basis of the unpurified nndecylenic a c i d -CCI4 product) Found24.09% Chlorine 24.3% Lead 167 grams Percent C1 28.8% Percent Pb= 25.1%Yield=167ggrarns EXAMPLE III Amyl ester of undecyZem'caczYL-CCM product.

Ninety-five grams of an. undecylenic acid-carbon tetrachloride: producthaving 34.4% chlorine and N. N. of 196.5; was mixed with- 44 grams ofisoamyl alcohol, 110 cc. of toluene and 1 gram of para-toluenesulfonicacid. The solution was refluxed for. five hours at 120 C. with theseparation of 5 cc. of water in a sidearm water trap. The solution waswater washed and topped to 150 C. at '2-3 mm., yielding 1'06 grams(about 7% yield) of aproduct which had'the following analysis:

Found (on the undecylenicacid) 5 Percent=Chlorine= 28;0%'

NeutralizationNum'ber=Nil Percent Chlorine =-28A%" Neutralization Number; 1;

EXAlVi'PL'Ji}v IV Undecylenic acid-chloroform product Three hundredandisixtyeight grams ('2 mols) of undecylenic acid and 1500 cc. of'chloroform. were heated at gentle. reflux (60-64 C.) for '72- hours withthe addition of 2 grams of benzoylperoxide every. hour during the dayexcept the back on the surface.

specificgravity of; 1.1315. at:-2'l. (3.1, was obtained.

Undecylenic; acid. at. the: same temperature. had;

6'" gravity of 0.030. The analysisior the product was as follows;

Found. Theory;- for- 0 15 01 6003 Percent Ohlorine=35 .1 vNeutralization Number 184 Bromine'AdditionValue=-Nil; 1

Percent Chlorine =29.7 Neutralization N umbcr= 172.- 3- Bromine AdditionValue=0.5

EXAMPLE V Oleic aoid-CC14 product Twov hundredeei'ghty-three. andfive-tenths (2835) gms. (approx; 1.mol)- of" oleic acid were: mixed with1413 gms. (approx. 9.1 mols) of car bonv tetrachloride; Rive grams ofbenzoyl peroxide were added andv the contents. of the flask were heatedto reflux; Reaction was continued;

for 98. hours with. the. addition of 2 grams: every hour of the dayexcept for the last hour of the day. when 5 gramsofi'benzoyl peroxidewereadded before heating and stirring overnight. Atotal. of

grams (.39 mol) of. benzoyl peroxide were. added. The pot temperatureduring, refluxwas 80 C. most of the time. Excess carbon tetrachlorideandsomebenzoicacid were removed by distillation to a pot temperature of1'5'0' '"C. under 9 mm. pressure. The residue: was then extracted ninetimes with 500 cc. portionsof a 50%. alcohol, solution in water toremove the remainder ofthe" benzoic acid. Topping of'the' product to C.at- 21mm. pressure gar/e405: grams; (9.312%. yield) ot, a. dark redviscous oil. which. had a; specific; gravity ati26f C..of. 1.151comparedwitha; gravity: ofr0.8862.for oleic acidr- Theanalysis of theprod1zuctiwasas follows:

Found Theory" for GwHnOllCOOH PercentChlorine=30:3' BromineAddition.Valuc,=1'.9r Neutralization Number;

Percent Ghlorine=32t6 EXAMPLE VI- Ol'eic acid-chloroformproduct Twohundredandeighty-twograms (L mol). of. oleicv acid and 1000 grams (8.3+mols) of chloroe form were mixed. and heated to reflux at 67-72? benzoylperoxide; The product was taken up in" ahigh" boiling hydrocarbonsolvent and topped to' C; pot temperature at2' mm. pressure toremovesolvent and benzoic acid. The. product was 3'73 grams (93% yield)ofa red oil hayingspecific gravity of.1.01.6. Theanalysis wasas'followsz Found Theory for OrsHuCliOOOH Percent Chlorine 14.85 BromineAddition Value=9.0 NeutralizationNumber=115.7.

Percent Ohloriue=26.5

Neutralization. Numher=l4d BrominehdditionValue=NiLNeutralizationNumben=128.4.

Bromine Addition-Value Nil 7 EXAMPLE VII Oleic acid-linolez'c acidmixture CCl4 product Two hundred and eighty-one grams of a mixture whichis comprised of approximately 40 parts of oleic acid and 60 parts oflinoleic acid were mixed with 400 grams of carbon tetrachloride and 2grams of benzoyl peroxide and then heated to reflux at 78-79 C. Reactionwas continued for 102 hours with the stepwise addition of 2 grams ofbenzoyl peroxide every hour of the day except the last hour of the daywhen 5 grams of benzoyl peroxide were added before heating and stirringovernight. A total of 86 grams (.35 mol) of benzoyl peroxide was added.The unreacted C014 was topped off under reduced pressure. The residuewas extracted with a 50/50 alcohol-water solution, taken up in 300 cc.of a high boiling hydrocarbon solvent and topped to 160 C. pottemperature at 2 mm. pressure to remove the solvent and benzoic acid.Four hundred and nine grams of a dark red oil with a specific gravity of1.064 at 32 C. were obtained. The analysis was as follows:

Percent chlorine=l8.04 Bromine addition value=12.2 Neutralizationnumber=114.5

This product is probably a polymer with about one 0013 group perdimerized fatty acid.

EXAMPLE VIII Preparation of the undecylenz'c acid-bromotrichloromethaneproduct One hundred and eight-four grams (1 mol) of undecylenic acid and1000 grams (5+ mols) of bromotrichloromethane were mixed and 2 grams ofbenzoyl peroxide were added. At 80 C. an exothermic reaction took placeand the temperature rose quickly to 104 C. An ice bath was applied tocontrol the vigorous reflux and the temperature went down to 70 C. Heatwas again applied and at 85 C. an exothermic reaction again took placebut to a lesser extent. An additional 2 grams of benzoyl peroxide (total.013 mol) were added and the reaction mass was held between 88 C. and 92C. for an hour.

The excess bromotrichloromethane and any unreacted undecylenic acid weredistilled, and benzoic acid from the catalyst was sublimed, by toppingto a maximum pot temperature of 170 C. at 2 mm. mercury pressure. Theresidue weighed 369 grams which represented a yield of 96.5% based on amonomeric addition product. The analysis was as follows:

Found Theory for CnHwBr 013C 0 OH Neutralization N umber=l47% BromineAddition Valne=l. 0 Percent Chlorine=24. 7 Percent Bromine=22. 0

Neutralization Number=l46 A Bronlce Addition Value=0. 0 PercentClilorine=27. 84 Percent Brominc=20. 0

terials contemplated by this invention as extreme pressure lubricantingredients, we have prepared and tested various compositions comprisedof the several reaction products described above and a hydrocarbonlubricant oil as the carrying agent. More specifically, we have preparedvarious lubricant blends from a mineral lubricating oil fraction havinga Saybolt Universal viscosity of 64 to 67 seconds at 210 F., to which aminor proportion of the product obtained by the reaction of thepolyhalomethanes with the unsaturated acids have been added. Theseblends were subjected to the Almen pin test (described by Wolf AndMougey, Proc. A. P. 1., 1932, pp. 118-130); the S. A. E. test (describedin S. A. E. Journal 39, 23-24, 1936) and the Timken test. These threetests are commonly accepted in the art as standards for determining theextreme pressure characteristics of a lubricant.

In the table given below we show the results obtained from the abovetests using the oil without the addition agent and samples of the sameoil blended with the compounds of the invention.

TABLE Cone. P f s. A. E. Timken Product Added In Oil, B Test (Lbs. Test(Lbs.

Percent Failed) Failed) Failed) None 4, 000 Less than Less than 2Ugdficylenic Acid- 10 30,000 520 55.

4. Ugcecylenic Acid- 5 30, 000 350 65.

Ugdlecylcnlc Acid- 1 6,000 280 Undecylenic Acid 5 9,000 300 H0013. Olel:Acid-C C14 10 0,000 324 Oleic AcldHC Ola. 10 5,000 Amyl ester, Undecy-10 7,000 80 1enicCCl4. Amy] Ester, Undecy- 5 5, 000 66 45.

lenic-CC14. Undecylenic Acid 10 30, 000 462+ Bl'CCla.

From the foregoing table it will be seen that the product compounds ofthis invention are highly efficient extreme pressure lubricant bases.The amount of these product materials which may be added to ahydrocarbon lubricant oil, or

other suitable carrying agent, to form an extreme pressure lubricantcomposition may be varied from about 0.5% to about 20% by weight.

Lubricating oil concentrates are also contemplated herein, suchconcentrates containing substantially larger amounts of the extremepressure ingredients than those just above mentioned. That is,relatively large amounts, upwards of about 20% weight, of the saidmaterials may be incorporated in an oil fraction and the oilconcentrates so obtained may thereafter be diluted with a suitablequantity of an oil prior to use to produce the desired operable ultimateconcentration.

Although it is generally preferred to use the characterizing ingredientsof the invention incorporated with ordinary petroleum type lubricationoils as the carrying agents therefor, it is not intended that theinvention be limited to any particular carrying or blending medium, butthe invention includes broadly extreme pressure lubricants containingthese ingredients dissolved, dispersed or emulsified in any othersuitable carrying medium, such for example as relatively non-viscouspetroleum hydrocarbons, such as kerosene, as well as fatty vegetable oranimal .oils, alcohols, esters, ethers, etc.

It is to be understood that the characterizing ingredients of theinvention may be used in the 9 carrying medium in combination with otheroil addition agents, such, for example, as sulfur type E. P. additives,oiliness agents, antioxidants, pour point depressants, detergents,viscosity index improving agents, etc.

As stated hereinbefore, the novel compounds of the invention are usefulchemical intermediates from which other valuable compounds may beprepared. Thus, the halogen in our compounds may be replaced by reactionwith various metal salts or may be eliminated as hydrohalogen acidyielding an olefin. The tricholoromethane group can be converted to anortho ester and to an acid. The acids, of course, will form metal orammonium salts or soaps which are useful as grease components forgreases subjected to extreme load conditions.

It is to be understood that while we have herein described compoundsobtained with certain specific materials, and have illustrated exemplarymethods of preparing such compounds, the invention is not limited to thespecific compounds described or to the specific methods of preparationthereof but includes such variations in reactants and procedure asfairly come within the scope of the appended claims.

This application is a division of our copending application, SerialNumber 34,827, filed June 23, 1948, now abandoned.

We claim:

1. As a new composition of matter, a compound of the general formulawhere R is selected from the group consisting of hydrogen, alkyl andalkenyl radicals, R is selected from the group consisting of hydrogen,metal and basic ion, m is an integer from 4 to 13, n is an integer from1 to 3, and where A and B are univalent radicals selected from the groupconsisting of CC13, -Cl and -Br, one of them always being --CC13, butnever both.

2. As a new composition of matter, a compound of the general formulawhere Ris alkyl, R is selected from the group consisting of hydrogen,metal and basic ion, m is an integer from 4 to 13, n is an integer from1 to 3 and where A and B are univalent radicals selected from the groupconsisting of -CC13, -Cl and -Br, one of them always being C'C1a, butnever both.

4. As a new composition of matter, the compound ClsC-CI-Ia-CHCl-(CHz)s-COOH 5. As a new composition of matter, the compound CC13CH2-CHBr(CH2) 8-COOH 6. As a new composition of matter, the compoundC13CCH2CHCl---(CH2) aCOO] 2Pb References Cited in the file of thispatent UNITED STATES PATENTS Number Name Date 2,262,813 Morway et alNov. 18, 1941 2,319,183 Badertscher May 11, 1943 2,425,426 Joyce Aug.12, 1947 2,449,547 Byrkit Sept. 21, 1948 2,561,516 Ladd et al. July 24,1951 2,568,859 Ladd et al. Sept. 25, 1951 OTHER REFERENCES Kharasch etal.: J. Am. Chem. Soc., vol. 68, p.

Kharasch: Science, 102, p. 128 (1945).

1. AS A NEW COMPOSITION OF MATTER, A COMPOUND OF THE GENERAL FORMULA